EP0856518B1 - Métallocènes, leur préparation et leur utilisation - Google Patents

Métallocènes, leur préparation et leur utilisation Download PDF

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EP0856518B1
EP0856518B1 EP98500022A EP98500022A EP0856518B1 EP 0856518 B1 EP0856518 B1 EP 0856518B1 EP 98500022 A EP98500022 A EP 98500022A EP 98500022 A EP98500022 A EP 98500022A EP 0856518 B1 EP0856518 B1 EP 0856518B1
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equal
chloro
silanediyl
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germanium
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EP0856518A1 (fr
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Luis Mendez Llatas
Antonio Munoz-Escalona Lafuente
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Repsol Quimica SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Definitions

  • the metallocene compounds field has experimented a big development since the first syntheses of these compounds in the fifties (G. Wilkinson et al., J. Am. Chem. Soc ., 1953, 75, 1011). This development is basically due to the large increase in the number of applications wherein these compounds are used. So, they can be used as catalysts of hydrogenation, epoxidation, double bond isomerization, ketons reduction, aldolic reaction, synthesis of different substituted olefins, etc., but their largest use is as catalyst components for olefin polymerization, as they can be activated for this use by alumoxanes or other non-coordinative anion precursors (for example boron compounds).
  • metallocenes of group 4 (Ti, Zr, Hf) in particular have been developed, but also metallocenes of groups 3, 5 and 6.
  • Metallocenes were prepared for working in very different conditions (solution, suspension, mass, gas phase, high pressure and temperature processes, etc.). They were used for polymerizing and copolymerizing simple a-olefins, basically ethylene and propylene, but also more complex olefins (cyclolefins, diolefins and also olefins with polar groups; for example W.A. Nugent et al., J. Am. Chem. Soc . 1989, 111, 6435; R.M. Waymouth et al., J. Am. Chem. Soc . 1992, 114, 9679; H Yasuda et al., Macromol.Chem.Phys , 1995, 196, 2417).
  • Chem., 1979, 173, 6270 as it influenced the reactivity of the metallocene not only for its own steric and electronic nature, but also for (1) influencing the monomer greater or smaller accessibility to the active center as the bridge largerly determines the angle spread between the cyclopentadienyl rings and (2) for preventing the free rotation of the rings and, therefore, determining the symmetry of the whole molecule. With this it has been obtained a better stability of certain metallocenes, a greater or smaller discrimination of the monomers that are incorporated into the polymer because of their size and the possibility of obtaining or not stereoregolar polymers starting from a-olefins (isotactic, syndiotactic, hemiisotactic).
  • EP-A-757053 discloses new metallocenes characterized by the following general formula : X m M(L-M 2 (R 1 R 2 )-A-ZR 3 o Hal p ) n , wherein M is a metal of group 4, 5 or 6 of the periodic table, each X is independently selected from hydrogen, halogen or a C 1 -C 40 carbon-containing rest; m is equal to 1, 2 or 3; n is equal to 1 or 2; each L is independently a ⁇ ligand, which coordinates to the central atom M; each M 2 is independently selected from silicon, germanium or tin; R 1 is a C 1 -C 20 carbon-containing group; R 2 is a C 1 -C 20 carbon-containing group or a ⁇ ligand, which coordinates to the central atom M; each A is independently a divalent C 1 -C 40 carbon-containing rest; each Z is independently selected from boron, silicon, germanium or tin; each R 3 is independently selected from hydrogen
  • This compounds are characterized by the presence of a hydrocarbon bridge connecting two silicon, germanium or tin atoms to whom the halogen atom is connected. This characteristic makes them expecially suitable in the preparation of supported catalysts. There is no mention of their possible use in the preparation of further functionalized metallocenes.
  • the invention object of the present application introduces a clear advantage as it develops even more the influence of the bridge in the metallocene structure, for providing this bridge with a functionality , that is to say a unity able to react with determined substrates.
  • the object of the introduction of this functionality is the possibility of modifying the metallocenes through that reactive center. This can allow, among other applications, a new simple method for obtaining new di- or polymetallocene compounds, these compounds being those which show more than one metallocene unit in their structure.
  • the fact of localizing the functionality in the bridge instead of other parts of the molecule has the advantage of maintaining this reactive position away from the catalytically active metallocene center.
  • organometallic compounds of transition metals of groups 3, 4, 5 or 6 of the periodic table of metallocene-type are characterized in that they have at least one union or bridge between the cyclopentadienyl type unities.
  • the bridge is characterized in that it shows at least one functionality, this being a Si-Y, Ge-Y or Sn-Y-type unity, preferably Si-Y, Y being halogen.
  • the invention preferably refers to metallocenes represented by the following formula (formula II): wherein:
  • This synthesis process of metallocenes with functionalized bridge can be realized in a temperature range between -20 and 300°C, preferably between 0 and 200°C, or at the reflux temperature of the used solvents system.
  • This process for the synthesis of metallocenes with functionalized bridge can be realized with or without protection from light.
  • a fit substrate is one that has at least one reactive group of type G-J, G representing an element of groups 14, 15, 16 or 17 and J representing an element of groups 1 (including hydrogen), 2 or 3.
  • reaction process between both reactive groups can be represented by the following equation wherein the symbol is used in this context to represent the union of said reactive groups with the rest of the compound wherein they are integrated; G, J, Y, E, Z and o are defined above.
  • metallocene derivatives can be obtained starting from functionalizated precursor metallocenes characterized by having one or various unities G-(E) o -Z .
  • Reactive groups G-J are, for example: hydroxy, amine, phosphino, thiol, hydroxy, amido, phosphido, thioxy, alkyl anions etc.
  • substrates containing these groups are: water, ammonia, silica, alumina, alcohols, phenols, silanols, thiols, primary and secondary amines, primary and secondary phosphines, hydrogen halides, alkylides or alcoxides or amidos or phenoxides or alcoxides or hydroxides of alkali or alcaliearth metals, or compounds that combine various unities among these, for example: aminoalchools, hydroxythiols, polyols, diols.
  • the possible compounds and materials obtained starting from the metallocenes functionalized according to the present invention are practically unlimited.
  • a particularly interesting case can be the obtaining of bimetallocene or polymetallocene derivatives obtained starting from the reaction between a substrate with two or more groups G-J and various metallocenes with different functionalized bridges.
  • What follows are some examples of the derivatives of the metallocenes functionalized in the bridge, as a clarification which does not imply any restriction.
  • R, M, Cp have the above defined meaning.
  • Si, O, N, S symbolize an atom of the corresponding element according to the periodic table.
  • Both the functionalized metallocenes object of the present invention and their derivatives, including those supported on inorganic solids, can be used in various functions, their use as catalyst components for ⁇ -olefins polymerization reactions in conjunction with one or various cocatalysts being a special case.
  • This example is useful for describing a zirconium metallocene with a functionalized bridge and its synthesis.
  • a solution of 30 ml (0.25 mol) of trichloromethylsilane and 250 ml of dry hexane is added to a suspension of 0.25 mol of CpTMSLi and 200 ml of hexane. Then, the reaction mixture is heated at the reflux temperature for 5 h. After cooling, the solid is filtered and washed with 200 more ml of hexane. From the union of the filtered product and the washing waters, after the elimination of the solvent in vacuum, a pale yellow oil that distils at 73-74°C (2 Torr) is obtained. The obtained product is mostly the isomer 1-(dichloro(methyl)silyl)-1-(trimethylsilyl)cyclopentadyene.
  • Mass spectrometry M + m / z (relative intensity) 373.9 (14%) 372.9 (8%), 371.9 (41%), 370.9 (18%), 369.9 (80%), 368.9 (36%), 367.9 (100%), 366.9 (30%), 365.9 (71%) [M + calculated for C 11 H 11 Cl 3 SiZr: 373.9 (13%), 372.9 (8%), 371.9 (41%), 370.9 (18%), 369.9 (77%), 368.9 (33%), 367.9 (100%), 366.9 (28%), 365.9 (73%)]
  • This example describes a hafnium metallocene with functionalized bridge and its synthesis.
  • Masses spectrometry M + m / z (relative intensity) 460.9 (4%), 459.9 (19.5%), 458.9 (19%), 457.9 (65%), 456.9 (50%), 455.9 (100%), 454.9 (60%), 453.9 (55%), 452.9 (31%), 451.9 (10%) [M + calculated for C 11 H 11 Cl 3 SiHf: 460.9 (4%), 459.9 (21%), 458.9 (19%), 457.9 (70%), 456.9 (45%), 455.9 (100%), 454.9 (54%), 453.9 (51%), 452.9 (28%), 451.9 (8%)].
  • This example describes the process for obtaining a bimetallocene compound starting from metallocenes with functionalized bridge.
  • This example describes the reaction between a metallocene with functionalized bridge and a monohydroxyl alcohol.
  • Masses spectrometry M + m / z (relative intensity) 446.0 (7%), 445.0 (6%), 444.0 (32%), 443.0 (19%), 442.0 (69%), 441.0 (39%), 440.0 (100%), 439.0 (45%), 438.0 (91%) [M + calculated for C 18 H 16 Cl 2 OSiZr: 446.0 (9%), 445.0 (8%), 444.0 (33%), 443.0 (20%), 442.0 (70%), 441.0 (38%), 440.0 (100%), 439.0 (44%), 438.0 (92%)].
  • This example describes the reaction between a metallocene with functionalized bridge and a diol.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Claims (9)

  1. Un composé métallocène caractérisé par la formule suivante :
    Figure 00310001
       où:
    Y est un halogène ;
    M est un métal de transition appartenant aux groupes 3, 4, 5 ou 6 de la classification périodique des éléments;
    chaque L est sélectionné indépendamment parmi une unité du type cyclopentadiényl, qui comprend de l'indényl ou du fluorényl, substitué ou pas, et les substituants étant identiques ou différents, unis à M par un liant π;
    Z est un groupe qui forme une union de type pont entre les deux unités L, et qui peut avoir entre 0 et 20 atomes de carbone et entre 0 et 5 atomes d'oxygène, de soufre, d'azote, de phosphore, de silicium, de germanium, d'étain ou de bore ;
    E est un groupe d'écartement qui unit Z et Y, et qui peut avoir entre 0 et 20 atomes de carbone et entre 0 et 5 atomes d'oxygène, de soufre, d'azote, de phosphore, de silicium, de germanium, d'étain ou de bore, et se caractérise en ce que sa structure comprend au moins un atome de silicium, de germanium ou d'étain, auquel est unit le substituant Y :
    o est un chiffre de valeur 0 ou 1;
    k est un chiffre de valeur 1, 2, ou 3;
    m est un chiffre supérieur ou égal à 2, qui coïncide avec l'état d'oxydation du métal de transition;
    j est un chiffre de valeur 0 ou 1 avec la condition que sa valeur soit 1 au moins une fois; quand j est égal à 1 et o est égal à 0, Z se caractérise en ce qu'il contient au moins un atome de silicium, de germanium, ou d'étain auquel est unit directement Y;    avec la condition que le composé ne corresponde pas à la formule générale Xm,M' (L'-M2(R'R2)-A'Z'R3 o,Halp, )n,    Où M' est un métal appartenant aux groupes 4, 5 ou 6 de la classification périodique des éléments, chaque X est sélectionné indépendamment parmi l'hydrogène, l'halogène ou un fragment qui contient du carbone C1-C40; m' est égal à 1, 2, ou 3; n' est égal à 1 ou 2; chaque L' est indépendamment un liant π, qui s'associe avec l'atome central M'; chaque M2 est sélectionné indépendamment parmi le silicium, le germanium ou d'étain; R' est un groupe qui contient du carbone C1-C20; R2 est un groupe qui contient du carbone C1-C20 ou un liant π, qui s'associe avec l'atome central M'; chaque A' est indépendamment un fragment divalent qui contient du carbone C1-C40; chaque Z' est sélectionné indépendamment parmi le bore, le silicium, le germanium ou l'étain; chaque R3 est sélectionné indépendamment parmi l'hydrogène ou un fragment qui contient du carbone C1-C20; o' est égal à 0, 1, ou 2; chaque Hal est sélectionné indépendamment parmi un atome d'halogène; p' est égal à 1, 2 ou 3.
  2. Un composé métallocène selon la revendication 1, caractérisé en ce qu'il correspond à la formule :
    Figure 00330001
       où;
    Y est un halogène;
    M est un métal de transition appartenant aux groupes 3, 4, 5 ou 6 de la classification périodique des éléments;
    chaque L est sélectionné parmi une unité de type cyclopentadiényl, qui comprend de l'indényl ou du fluorényl, substitué ou pas, et les substituants étant identiques ou différents, unis à M par un liant π;
    Q est un élément des groupes 13, 14 ou 15 ;
    E est un groupe d'écartement qui unit Q et Y, et qui peut avoir entre 0 et 20 atomes de carbone et entre 0 et 5 atomes d'oxygène, de soufre, d'azote, de phosphore, de silicium, de germanium, d'étain ou de bore, et se caractérise en ce que sa structure comprend au moins un atome de silicium, de germanium ou d'étain, auquel est uni le substituant Y;
    R est un atome d'hydrogène, d'halogène, d'hydrocarbure halogéné, d'hydrocarbure halogéné substitué, d'alkyl C1-C20, d'alcényl C2-C20, d'aryl C6-C20, d'alkyl-aryl C7-C40, d'aryl-alkyl C7-C40, d'aryl-alcényl C1-C20, d'alcoxy, de siloxy et des combinaisons de ces derniers;
    A, identiques ou différents entre eux, sont des groupes pont entre les unités L et Q composés aussi bien seulement par un atome divalent du groupe 16, de préférence -O-, que par un élément trivalent monosubstitué du groupe 15, de préférence >N-R, R étant tel qu'il a été défini antérieurement, ou un élément tétravalent disubstitué du groupe 14, de préférence >C(R)2 ou >Si(R)2, R étant tel qu'il a été défini antérieurement, ou par une chaíne de 2 ou plusieurs atomes substitués ou pas, cette chaíne étant de préférence du type -C-C-, -C-Si-, -Si-Si-, -Si-O-, -C-O-, -C-N-, -C-C-C-, -C-Si-C-, -Si-O-Si-;
    o est un chiffre de valeur 0 ou 1;
    k est un chiffre de valeur 1, 2 ou 3;
    m est un chiffre supérieur ou égal à 2 et qui coïncide avec l'état d'oxydation du métal de transition;
    p, n, l sont des chiffres de valeur 0 ou 1;
    j est un chiffre de valeur 0 ou 1 avec la condition que sa valeur soit 1 au moins une fois; quand j est égal à 1 et o est égal à 0, Q est un atome de silicium, de germanium ou d'étain;
       avec la condition que le composé ne corresponde pas à la formule générale Xm, M' (L'-M2(R'R2)-A'-Z'R3 o'Halp')n'    où M' est un métal appartenant aux groupes 4, 5 ou 6 de la classification périodique des éléments, chaque X est sélectionné indépendamment parmi l'hydrogène, l'halogène ou un fragment qui contient du carbone C1-C40; m' est égal à 1, 2 ou 3; n' est égal à 1 ou 2; chaque L est indépendamment un liant π, qui s'associe avec l'atome central M'; chaque M2 est sélectionné indépendamment parmi le silicium, le germanium ou l'étain; R' est un groupe qui contient du carbone C1-C20; R2 est un groupe qui contient du carbone C1-C20 ou un liant π, qui s'associe avec l'atome central M'; chaque A' est indépendamment un fragment qui contient du carbone C1-C40 divalente; chaque Z' est sélectionné indépendamment parmi le bore, le silicium, le germanium ou l'étain; chaque R3 est sélectionné indépendamment parmi l'hydrogène ou un fragment qui contient du carbone C1-C20; o' est égal à 0, 1 ou 2; chaque Hal est sélectionné indépendamment parmi un atome d'halogène; p' est égal à 1, 2 ou 3.
  3. Un procédé de synthèse de composés métallocènes selon la revendication 1, caractérisé en ce qu'ils sont obtenus grâce au procédé suivant :
    Figure 00350001
       où:
    Y, Z, L, E, M, j, m y o sont tels qu'ils ont été définis antérieurement;
    S est un groupe ressortissant uni à l'anneau cyclopentadiényl, de préférence formé par une unité T(R4)3; T étant du silicium, du germanium ou de l'étain et R4 est un alkyl C1-C20.
  4. Un procédé selon la revendication 3 où chaque S représente séparément un groupe Si(CH3)3 ou Sn(CH3)3.
  5. Un procédé selon la revendication 3 où l'union L-S représente une union ionique, de type s ou de type p, ou des combinaisons de ces derniers; et l'union L-M représente une union de caractère π de type élevé.
  6. Un procédé de synthèse de dérivés du métallocène caractérisé en ce que l'on fait réagir le pont fonctionnel des composés des revendications 1 ou 2 avec des substrats dont la structure comprend un ou plusieurs groupes réactifs représentés par G-J, où G est un élément des groupes 14, 15, 16 ou 17 et J représente un élément des groupes 1 (y compris l'hydrogène), 2 ou 3.
  7. Un procédé selon la revendication 6 caractérisé en ce que G-J est sélectionné parmi : hydroxy, amine, phosphine, tyol, hydroxy, amide, phosphure, tioxy.
  8. Un procédé selon la revendication 6 caractérisé en ce que le substrat est un polyol.
  9. Un procédé selon la revendication 6 caractérisé en ce que le substrat est un diol.
EP98500022A 1997-02-01 1998-01-29 Métallocènes, leur préparation et leur utilisation Expired - Lifetime EP0856518B1 (fr)

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JP (1) JP3390133B2 (fr)
AT (1) ATE236914T1 (fr)
DE (1) DE69813058T2 (fr)
ES (1) ES2192760T3 (fr)
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US10968290B2 (en) 2017-03-28 2021-04-06 Exxonmobil Chemical Patents Inc. Metallocene-catalyzed polyalpha-olefins

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ES2154017T3 (es) * 1996-10-31 2001-03-16 Repsol Quimica Sa Sistemas cataliticos para la polimerizacion y copolimerizacion de alfa-olefinas.
EP0856524A1 (fr) 1997-02-01 1998-08-05 Repsol Quimica S.A. Composants catalytiques hétérogènes pour la polymérisation des oléfines, procédé pour leur préparation et leur utilisation
US7148173B2 (en) 1998-04-27 2006-12-12 Repsol Quimica, S.A. Catalytic systems for the polymerization and copolymerization of alpha-olefins
ES2190187T3 (es) * 1998-04-29 2003-07-16 Repsol Quimica Sa Componentes de metaloceno funcionalizados, procedimiento de sintesis y uso.
DE69916358T2 (de) * 1998-04-29 2005-04-21 Repsol Quimica Sa Verfahren und Verwendung von heterogenen Katalysatorbestandteilen für die Olefinpolymerisation
US6706827B1 (en) * 1998-06-08 2004-03-16 Samsung Atofina Co. Ltd. Metallocene catalysts for olefin or styrene polymerization and polymerization method using the metallocene catalysts
AU764177B2 (en) 1998-12-18 2003-08-14 Univation Technologies Llc Haloaryl containing group 13 substituents on bridged metallocene polyolefin catalysts
KR100690345B1 (ko) * 2004-09-03 2007-03-09 주식회사 엘지화학 담지 메탈로센 촉매, 그 제조방법 및 이를 이용한폴리올레핀의 제조방법
CN106008767A (zh) * 2016-05-23 2016-10-12 北京化工大学 醇氧亚甲基桥联双金属半茂催化剂及制备方法与应用
CN106046208B (zh) * 2016-05-23 2019-03-29 北京化工大学 硅羟氧基桥联的双金属半茂催化剂及制备方法与应用
WO2018182984A1 (fr) * 2017-03-28 2018-10-04 Exxonmobil Chemical Patents Inc. Composés métallocènes

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EP0816395B1 (fr) * 1994-04-11 2000-07-19 Mitsui Chemicals, Inc. Procédé pour préparer une composition polymère de propène et composition polymère de propène
DE19527652A1 (de) * 1995-07-28 1997-01-30 Hoechst Ag Metallocenverbindung
ES2120868B1 (es) * 1995-08-03 2000-09-16 Repsol Quimica Sa Sistema de catalizadores hetereogeneos tipo metalogeno, para procesos de obtencion de poliolefinas.
IT1283010B1 (it) * 1996-05-15 1998-04-03 Enichem Spa Complesso metallocenico supportato e procedimento per la sua prepa- razione

Cited By (1)

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Publication number Priority date Publication date Assignee Title
US10968290B2 (en) 2017-03-28 2021-04-06 Exxonmobil Chemical Patents Inc. Metallocene-catalyzed polyalpha-olefins

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ES2192760T3 (es) 2003-10-16
US6018064A (en) 2000-01-25
JP3390133B2 (ja) 2003-03-24
ATE236914T1 (de) 2003-04-15
NO980412L (no) 1998-08-03
DE69813058T2 (de) 2004-02-19
DE69813058D1 (de) 2003-05-15
NO980412D0 (no) 1998-01-30
NO323005B1 (no) 2006-12-18
PT856518E (pt) 2003-08-29
JPH10226693A (ja) 1998-08-25

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